Nanofiber electrodes for batteries and methods of making nanofiber electrodes

ABSTRACT

Provided herein is a battery and an electrode. The battery may include two electrodes; and an electrolyte, wherein at least one electrode further includes: a nano-scale coated network, which includes one or more first carbon nanotubes electrically connected to one or more second carbon nanotubes to form a nano-scale network, wherein at least one of the one or more second carbon nanotubes is in electrical contact with another of the one or more second carbon nanotubes. The battery may further include an active material coating distributed to cover portions of the one or more first carbon nanotubes and portions of the one or more second carbon nanotubes, wherein a plurality of the one or more second carbon nanotubes are in electrical communication with other second carbon nanotubes under the active material coating. Also provided herein is a method of making a battery and an electrode.

BACKGROUND

With the ever increasing use of batteries, consumers desire betterperformance in terms of speed of charging and discharging, as well ascharge capacity from their batteries.

Carbon nanotubes (and other nanosized objects) are becoming more popularin manufacturing as supply increases. However, methods for coatingcarbon nanotubes have been limited to traditional coating techniques,which lead to non-uniform coating characteristics, especially when thecarbon nanotubes are networked prior to coating.

SUMMARY

Provided herein is a fast fibril battery that can have both high powerdensity, which can lead to fast charging and discharging properties, andhigh energy density, which can be reflected as increased capacity. Fastcharging and discharging properties can be provided by utilizingconductive nanofibers and nanoscale active materials to provideelectrodes with short distances between the current collector and theactive materials (e.g., the nanoscale active materials). High chargecapacity can be provided by utilizing high surface area supports (e.g.,the nanofibers), creating networks with large and continuous porosity,in order to hold a greater quantity of active materials.

Also provided herein is an electrode, which includes a nano-scale coatednetwork, which includes one or more first carbon nanotubes electricallyconnected to one or more second carbon nanotubes to form a nano-scalenetwork, wherein at least one of the one or more second carbon nanotubesis in electrical contact with another of the one or more second carbonnanotubes. The electrode further including an active material coatingthat covers at least a portion of the one or more first carbon nanotubesand does not cover the one or more second carbon nanotubes to form thenano-scale coated network.

Also provided herein is a battery, which includes two electrodes; and anelectrolyte, wherein at least one electrode further includes: anano-scale coated network, which includes one or more first carbonnanotubes electrically connected to one or more second carbon nanotubesto form a nano-scale network, wherein at least one of the one or moresecond carbon nanotubes is in electrical contact with another of the oneor more second carbon nanotubes. The battery further including an activematerial coating distributed to cover portions of the one or more firstcarbon nanotubes and portions of the one or more second carbonnanotubes, wherein a plurality of the one or more second carbonnanotubes are in electrical communication with other second carbonnanotubes under the active material coating.

Also provided herein is an electrochemical capacitor which includes afirst electrode, which includes a nano-scale coated network, whichfurther includes one or more first carbon nanotubes electricallyconnected to one or more second carbon nanotubes to form a nano-scalenetwork. The electrochemical capacitor has at least one of the one ormore second carbon nanotubes is in electrical contact with another ofthe one or more second carbon nanotubes; and an active material coatingdistributed to cover portions of the one or more first carbon nanotubesand portions of the one or more second carbon nanotubes. Theelectrochemical capacitor also having a plurality of the one or moresecond carbon nanotubes are in electrical communication with othersecond carbon nanotubes under the active material coating; a secondelectrode; and an electrolyte.

Also provided herein is a battery, which includes two electrodes withdifferent electrode chemistries, wherein one of said electrodes furtherincludes carbon nanotubes (CNTs), said CNT containing electrode havingvolume porosity greater than 50%. The CNT electrode of the batteryfurther including less than 25% CNTs by weight. The battery, whendischarged at ambient conditions at a 1 C rate, having a cell voltagegreater than 80% of the theoretical voltage, said battery having arecharge efficiency, when recharged at 2 C rate, of greater than 95%.

Also provided herein is a method of forming a battery, which includesproviding a first electrode, wherein forming the first electrode furtherincludes: providing first carbon nanotubes; providing second carbonnanotubes; and coating the first carbon nanotubes with a nanoscalesubstance to form coated carbon nanotubes. The method further includingforming a network of the coated carbon nanotubes and the second carbonnanotubes; providing a first electrolyte; and redistributing thenanoscale substance onto the network in the first electrolyte to formthe first electrode. The method further including providing a secondelectrolyte; providing a second electrode; and providing the first andthe second electrode in the second electrolyte to form a battery,wherein the first electrolyte and the second electrolyte are differentelectrolytes.

Also provided herein is a method of forming a battery, which includesproviding a first electrode, wherein forming the first electrode furtherincludes: providing first carbon nanotubes; providing second carbonnanotubes; and coating the first carbon nanotubes with a nanoscalesubstance to form coated carbon nanotubes. The method further includingforming a network of the coated carbon nanotubes and the second carbonnanotubes in the first electrolyte; providing a first electrolyte; andredistributing the nanoscale substance onto the network in the firstelectrolyte to form the first electrode. The method further includingproviding a second electrolyte; providing a second electrode; andproviding the first and the second electrode in the second electrolyteto form a battery, wherein the first electrolyte and the secondelectrolyte are different electrolytes, and the first electrolyte andthe second electrolyte comprise aqueous, ionically conductiveelectrolytes.

Also provided herein is a method of forming a battery, which includesproviding a first electrode, wherein forming the first electrode furtherincludes: providing first carbon nanotubes; providing second carbonnanotubes; and coating the first carbon nanotubes with a nanoscalesubstance to form coated carbon nanotubes. The method further includingforming a network of the coated carbon nanotubes and the second carbonnanotubes; providing a first electrolyte; and redistributing thenanoscale substance onto the network in the first electrolyte to formthe first electrode. The method further including providing a secondelectrolyte; providing a second electrode; and providing the first andthe second electrode in the second electrolyte to form a battery,wherein the first electrolyte and the second electrolyte are differentelectrolytes and the second electrolyte further includes an electrolytewith a pH level between 7 and 12.5.

Also provided herein is a method of forming an electrode, which includesproviding first carbon nanotubes; providing second carbon nanotubes; andcoating the first carbon nanotubes with a nanoscale substance to formcoated carbon nanotubes. The method further including providing a localbuffer; forming a network of the coated carbon nanotubes, the secondcarbon nanotubes, and the local buffer; providing an electrolyte; andredistributing the nanoscale substance onto the network in theelectrolyte to form the electrode.

Also provided herein is a method of forming a battery, which includesproviding a first electrode, wherein forming the first electrode furtherincludes: providing first carbon nanotubes; providing second carbonnanotubes; and coating the first carbon nanotubes with a nanoscalesubstance to form coated carbon nanotubes. The method further includingproviding a local buffer; forming a network of the coated carbonnanotubes, the second carbon nanotubes, and the local buffer; providinga first electrolyte; and redistributing the nanoscale substance onto thenetwork in the first electrolyte to form the first electrode. The methodfurther including providing a second electrode; and providing the firstand the second electrode in the second electrolyte to form a battery,wherein the providing the local buffer further includes providing anoxide, a hydroxide, or a carbonate in solid form.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated and constitute a partof this specification, illustrate an embodiment of the invention. In thedrawings,

FIG. 1 is an overview illustration of a bulk volume with nanofibers andthick fibers used as support for an active material;

FIG. 2 is an overview illustration of an example method by which anelectrode may be formed;

FIGS. 3A-3F are example illustrations for forming an electrode by theexample method of FIG. 2;

FIG. 3G is an example illustration for forming a battery using theelectrode from the example method of FIG. 2;

FIG. 4 is a Scanning Electron Microscope (SEM) image of a network ofnanofibers;

FIG. 5 is an SEM image of nanofibers including active material thereonprior to redistribution of the active material within the nanofibers;

FIG. 6 is an SEM image of nanofibers including active material thereonafter redistribution of the active material within the nanofibers;

FIG. 7 is an example flowchart of a step of the example method of FIG.2;

FIGS. 8A-8B are example illustrations of nanofibers and active materialwhen the active material is redistributed among the nanofibers;

FIG. 9 is an example graphical illustration of charge-discharge resultsfor an example nanofiber-nanoscale active material electrode before andafter redistribution of the active material;

FIG. 10 is an example graphical illustration of discharge results for anexample nanofiber-nanoscale electrode containing Ni compounds;

FIG. 11 is an example graphical illustration of discharge results for anexample nanofiber-nanoscale electrode containing Zn compounds; and

FIG. 12 is an example graphical illustration of discharge results forexample nanofiber-nanoscale electrodes after 2 charge-discharge cyclesas separate electrodes, 9 charge-discharge cycles as separateelectrodes, and 18 charge-discharge cycles as a battery cell (i.e.,combined electrodes).

DETAILED DESCRIPTION

The following detailed description refers to the accompanying drawings.The same reference numbers in different drawings may identify the sameor similar elements. Also, the following detailed description describesembodiments of the invention and is not intended to limit the invention.Instead, the scope of the invention is defined by the appended claimsand equivalents.

A. OVERVIEW

As described herein, a fast fibril battery with fast charging anddischarging properties and high charge capacity can be provided by usingsmaller scale supports and active materials than traditional batteries.By providing smaller scale supports and active materials, electrontransport distances between supports and active materials can be madeshorter and thus provide a higher rate of charge and discharge.Currently, support structures, such as grids, are used to hold activematerials to form electrodes for batteries. The surfaces of the grid arecoated with a layer of active material; the layer is usually made ofsmaller particles. The electrons from the grid travel through the layerof the active material, which is usually much less conductive than thegrid, to reach the actual place of the electrochemical reaction on theborder between the active material particle and the electrolyte. Theresistance of the active material layer is the limiting factor in thespeed and power characteristics of a battery. To reduce the resistanceof the active layer, conductive materials are usually added to thelayer, such as carbon black, carbon fibers and nanofibers, and othertypes of conductive additives.

Another way to reduce the resistance of the active material layer is toreduce the thickness of the active material layer. When the thickness ofthe active material layer is reduced on a given grid, the overall amountof the active material will be reduced too, which will result in a lowercapacity of the battery. In order to maintain the same capacity with thereduced thickness of the active material layer, the surface area of thegrid may be increased by using, for example, a nanoscale grid.

Additionally, current batteries tend to trade high speed (i.e., fastcharging and discharging properties) and high capacity for size (i.e.,larger batteries for higher capacities) or flammability (i.e., morevolatile battery chemistries). With the concern for weight and safety asa trade-off for speed and capacity, most battery designers are forced tomake undesirable decisions that lead to compromises that can beunacceptable (e.g., explosiveness or flammability in high speed, highcapacity, lightweight batteries, or safety with lower speed, lowercapacity, and/or heavier weighted batteries).

Provided herein are electrodes that can provide high speed, highcapacity, lightness, and safety in batteries. These electrodes canutilize properties of nanofibers and nanoscale active materials, inconjunction with a current collector, to increase the speed and capacitywithout additional weight and/or additional safety concerns.

As used herein, the term current collector can include metal or otherconductive materials (e.g., carbon) and can be mesh, foil, plate, grid,etc. in structure. Additionally, the current collector is electricallyconnected to the load. Further information about current collectors canbe found in, for example, “Handbook of Batteries and Fuel Cells,” ed.David Linden, McGraw Hill Inc., 1984, which is incorporated in itsentirety by reference.

Increased speed can be implemented by providing a fast fibril batterythat utilizes nanofibers and nanoscale active materials. By providingelectrodes with nanoscale active materials located on nanofibers toallow for short electrical pathways between the nanoscale activematerials and a current collector (e.g., the nanoscale supportmaterial)) fast charging and discharging properties can be achieved.While not wishing to be bound by theory, it is believed that thethickness of the active material, which is poorly conductive, controlsthe rate of both charging and discharging reactions. By providing a thinlayer of active material (i.e., nanoscale active material on conductivenanoscale fibers), this limitation can be controlled and the distancethat an electron must travel through the active material (and thus, thetime to travel this distance) can be reduced. A fast fibril battery canalso have a higher capacity than other high power density batteries,such as thin film batteries, because the high porosity of the nanoscaleconductive support (i.e., the nanofibers) can allow a substantial volumeof the battery to be active material.

FIG. 1 depicts a bulk volume with nanofibers 110 and thicker fibers 120used as supports for an active material. As illustrated in FIG. 1, thinlayers of active material on nanofibers 110 provide more capacity thanthin layers of active material on thicker fibers 120 in the same bulkvolume.

Batteries include electrodes in an electrolyte. The electrodes includean anode and a cathode. During discharge, the chemical compounds, or“active material,” in an anode undergoes an oxidation reaction torelease one or more electrons, while the active material in a cathodeundergoes a reduction reaction to combine free electrons with ions. Thetype of active material can be selected based upon the half-cellpotential of two electrode chemistries. For example, electrodes may beselected based on potentials that differ from each other as much aspossible (i.e., one electrode may have a positive potential, and theother electrode may have a negative potential vs. a standard hydrogenelectrode (SHE)). For example, a battery may contain two electrodes witha potential difference between 0.5V and 3V. The anode and cathode worktogether to provide electrical energy via their chemical reactions.

The capacity of a battery depends upon the electrodes' energy density(i.e., the amount of energy that the active material in each electrodecan hold), as well as engineering factors, such as the weight of thepackaging, weight of current collectors and membranes, etc., and thespeed or power density of the battery depends upon the rate at whichenergy producing chemical reactions can be conducted (i.e., the speedthat electrical energy can be provided by the active material in eachelectrode).

The energy density can be determined by the types of active material andthe amount of active material. For this reason, particular types ofactive material (i.e., chemical compounds) are superior based on theparticular application. For example, lithium-ion batteries can be usedfor lightweight, high-performance applications, such as mobile devicesand computers as they have a desirable energy density for thesehigh-performance applications. Other batteries, such as lead-acid, havelower energy densities, so cannot be used to power lightweight,high-performance applications due to their higher weight. On the otherhand, for lower cost, high reliability, lower energy density requirementapplications, such as automotive SLI (starting, lighting, ignition)batteries, the lower cost and acceptable weight can make lead-acidbatteries more desirable than lithium-ion batteries.

Increasing the energy density of a battery can be accomplished byproviding more active material for a given space. In one implementation,less volume can be allocated to a support and more volume can beallocated to active material by using smaller support structures, suchas nanofibers or preferably, networks of nanofibers. Similarly,eliminating the current collector by using a conductive support can alsoincrease the energy density of a battery.

As described in U.S. Pat. No. 6,205,016 and its divisional U.S. Pat.Nos. 6,491,789, 6,031,711, and 6,099,960, all of which are explicitlyincorporated by reference, nanofibers can be used in electrochemicalcapacitors (ECs). ECs generally have much lower energy density thanbatteries. They store energy in an electric field between usually porouselectrodes separated by an ionically conductive electrolyte. Thuselectrochemical capacitors can store energy essentially only as surfacecharge while, batteries, on the other hand, store energy correspondingto a chemical reaction in a cell, and discharge energy based on achemical reaction associated with passage of a certain number ofelectrons or faradays per mole of reactants.

Increasing the energy density of the active material can also beaccomplished by distributing the active material throughout theconductive support network. In one implementation, increasing the energydensity of active material can be done by coating a conductive supportsystem with active material. For example, as illustrated in FIG. 2, afast fibril electrode can be provided in one embodiment by examplemethod 200.

B. METHOD OF MAKING AN ELECTRODE

FIG. 2 illustrates an example method 200 by which an electrode may beformed. FIGS. 3A-3F are example illustrations for forming an electrodeby method 200 of FIG. 2. FIG. 3G is an example illustration for forminga battery using the electrode from method 200 of FIG. 2.

Method 200 can include providing nanofibers in step 210. In oneimplementation, the nanofibers can be provided in a liquid medium or inanother media, such as air.

For example, as illustrated in FIG. 3A, first nanofibers 310 and secondnanofibers 315 can be provided in a first vessel 320. Nanofibers 310,315 may be the same or different sized (i.e., diameter, length/diameterratio, agglomeration size, etc.) nanofibers and may be formed of thesame or different types of materials within nanofibers 310 andnanofibers 315, respectively, or between nanofibers 310 and nanofibers315. For example, nanofibers 310 and nanofibers 315 may be single wallor multi-wall nanotubes, and may further include solid nanoscale fibers,fishbone nanoscale fibers, etc. In one embodiment, one or morenanofibers in nanofibers 315 may include the same or differentnanofibers (and microfibers and/or macrofibers) compared to one or morenanofibers in nanofibers 310 or compared to one or more nanofibers inother nanofibers 315.

Additionally, nanofibers 310, 315 may be produced in the same ordifferent batches, which may also yield variations in size, shape, orstructure. In one embodiment, nanofibers 310 and nanofibers 315 aresimilar within each group of nanofibers 310 and nanofibers 315,respectively. In one embodiment, nanofibers 310 and nanofibers 315 maybe similar in size and shape throughout nanofibers 310 and nanofibers315. The various shapes, sizes, and structures for nanofibers 310, 315are further discussed below.

Nanofibers 310, 315 may be provided in liquid medium 325 that can allownanofibers 310, 315 to self-assemble (i.e., aggregate or agglomerate) orremain independent (i.e., maintain a certain spacing distance) fromother nanofibers 310, 315. In one embodiment, liquid medium 325 caninclude a liquid vehicle, such as an aqueous solution or an electrolyte.For example, liquid medium 325 may be water. Further discussion onnetworking of nanofibers may be found in U.S. Pat. Nos. 6,099,965,7,923,403, and U.S. Patent Application Publication No. 2008/0176052 A1,which are incorporated herein in their entireties.

FIG. 4 is a Scanning Electron Microscope (SEM) image of a network ofnanofibers. As illustrated in FIG. 4, nanofibers 310, 315 may benetworked or entangled to form one or more aggregations. Furtherdiscussion of nanofibers 310, 315 follows below.

Method 200 can also include depositing an active material on firstnanofibers 310 to form coated nanofibers in step 220. The activematerial, as discussed further below, may be any material capable ofproviding an acceptable energy density and potential for a batteryelectrode, such as an electrochemically active nanoscale solidsubstance, as further discussed below. In one implementation, depositionof the active material may occur by separating first nanofibers 310 fromsecond nanofibers 315, such that only first nanofibers 310 (or secondnanofibers 315) may be subjected to the deposition of the activematerial to form coated nanofibers, while second nanofibers 315 mayremain non-coated nanofibers. While the active material is deposited onfirst nanofibers 310 to coat nanofibers in step 220, other materials,such as nanoscale substances may also be deposited on first nanofibers310. For example, local buffers or other nanoscale substances may alsobe deposited, as further discussed below.

For example, as illustrated in FIG. 3B, first nanofibers 310 can beplaced in second vessel 340, while second nanofibers 315 can be placedin third vessel 350. Active material 330 may be deposited on firstnanofibers 310 in second vessel 340, while nanofibers 315 in thirdvessel 350 may remain free of active material 330. Deposition of activematerial 330 can be done by any method that allows active material 330to adhere to a surface of nanofibers 310. For example, deposition canoccur in a liquid phase by chemical or electrochemical deposition. Asanother example, deposition can occur in a gas phase by chemical vapordeposition or physical vapor deposition. In one implementation, activematerial 330 may include an electrochemically active nanoscale solidsubstance, such as one or more of hydroxides, carbonates, fluorides,sulfates, oxalates, phosphates of one or more compounds, such as Ni, Zn,Cd, Fe, Pb, Mn, Co, Ag, Al, or Mg.

In another implementation, deposition of the active material may occurtogether with providing a local buffer. A local buffer can include anadditive that would moderate the pH of the neutral electrolyte (i.e.,“neutral” being a pH between 7 and 12.5, preferably between 9 and 11.5for the active materials 330 discussed herein), which may be providedfor the operation of the battery.

Method 200 can also include combining first nanofibers 310 coated withactive material 330 (from step 210 or the like) and second nanofibers315, which are not yet coated, in step 230. In one implementation, firstnanofibers 310 with active material 330 coating and second nanofibers315 may be combined by physically mixing them together in a liquidvehicle. For example, they can be mixed by any means, such as by using amixer, an agitator, a sonicator, or an ultrasonicator. In anotherimplementation, they can be mixed in a dry state by any means, such as amixer, a blender, or a mill, where the mill can mix them by milling theactive materials and the nanofibers together in any kind of highintensity device, including, but not limited to a ball mill or rod mill,colloid mill or microfluidizer in a continuous or a batch operation.

For example, as illustrated in FIG. 3C, nanofibers 310 with coating 330from second vessel 340 may be combined with non-coated nanofibers 315from third vessel 350.

In one example, as illustrated in FIG. 3D, first nanofibers 310 withcoating 330 and second nanofibers 315 can be networked together to forman electrically conductive network of nanofibers with electricalcommunication areas 360. By combining first nanofibers 310 with activematerial 330 and second nanofibers 315, electrical conductivity betweenfirst nanofibers 310 and second nanofibers 315 can be provided withinelectrical communication areas 360. While not wishing to be bound bytheory, it is believed that the electrical contacts between nanofibers315 will not be hindered by active material 330. Also, because of aplurality of these electrical contacts, the overall network can be veryconductive.

For example, as illustrated in FIG. 5, which is an SEM image ofnanofibers including active material thereon prior to redistribution ofthe active material within the nanofibers, a network of first nanofibers310 with active material 330 (i.e., nanofibers 310 with active material330 located on the surface) and second nanofibers 315 (i.e., nanofiberswithout active material 330) may be provided. As shown in FIG. 5, activematerial 330 may be present on first nanofibers 310 and not present onsecond nanofibers 315.

Method 200 can include redistributing active material 330 throughout thenetwork in step 240. In one implementation, redistribution of activematerial 330 can be provided by recrystallizing active material 330 fromactive material 330 on the surface of second nanofibers 310 to thesurface of first nanofibers 315. In another implementation,redistribution of active material 330 may be provided via electricalcharge and discharge.

For example, as illustrated in FIG. 3E, active material 330 from coatednanofibers 310 can be redistributed onto a portion of the previouslynon-coated nanofibers 315 to redistribute active material 330.Advantageously, in one implementation, active material 330 from coatednanofibers 310 can provide coverage of the surface of coated nanofibers310 and coverage of the surface of the previously non-coated nanofiber315 such that electrolytes that may be brought into contact with coatednanofibers 310 and the previously non-coated nanofiber 315 would notcontact either of the underlying nanofibers 310, 315.

By providing active material 330 directly on nanofibers 310, 315,electrical conduction paths between nanofibers 310, 315 and activematerial 330 can be reduced in length, thus leading to increasedelectrical conduction speed through a resulting electrode.

In one implementation, as illustrated in FIG. 6, which is an SEM imageof nanofibers including active material thereon after redistribution ofthe active material within the nanofibers, the coating from coatednanofibers 310 can move to cover large areas of nanofibers 310, 315 withdeposits by distributing active material 330 from first coatednanofibers 310 and to previously non-coated second nanofibers 315.

One implementation is illustrated in FIG. 7, which is an exampleflowchart of step 240 of method 200 of FIG. 2, and in FIG. 8A, which isan example illustration of nanofibers 310, 315 and active material 330when active material 330 is redistributed among the nanofibers 310, 315.In FIGS. 7 and 8A, redistributing active material 330 can occur byproviding an electrical charge to nanofiber network 810, which includesfirst (i.e., coated) nanofibers 310 and second (i.e., non-coated)nanofibers 315, in sub-step 710 of step 240. By providing an electricalcharge, some of active material 330 can be released from firstnanofibers 310 as released active material 820. Released active material820 can be released into areas among coated first nanofibers 310 andnon-coated second nanofibers 315.

Redistribution of released active material 820 from first nanofibers 310to second nanofibers 315 can occur in sub-step 820. It is believed thatreleased active material 820 will deposit onto the mostelectrochemically active areas of second nanofibers 315, which should bethe non-coated surfaces of second nanofibers 315. It is also believedthat while the non-coated areas of second nanofibers 315 are coated withreleased active material 820, the newly coated areas will become lesselectrochemically active and less attractive to released active material820 compared to non-coated areas of second nanofibers 315. Eventually,the non-coated areas of second nanofibers 315 can become coated and theelectrochemical activity of first nanofibers 310 and second nanofibers315 should reach equilibrium from the redistribution of released activematerial 820.

Alternatively, other mechanisms can be used to release active material330 from coated first nanofibers 310, as released active material 820for deposition on second nanofibers 315. For example, the network ofcoated nanofibers 310 with active material 330 and uncoated nanofibers315 can be subjected to repeated heating and cooling cycles in a liquidvehicle. Active material 330 can be partially released as releasedactive material 820 during a heating cycle and re-deposited in differentlocations during the cooling cycle.

Next, as illustrated in FIG. 8B, which is an example illustration ofnanofibers 310, 315 and active material 330 when active material 330 isredistributed among nanofibers 310, 315, nanofiber network 810, whichcan be an agglomeration or aggregation of first nanofibers 310 andsecond nanofibers 315, can be made accessible to released activematerial 820. A coated nanofiber network 830 may be formed by allowingreleased active material 820 to attach to non-coated second nanofibers315 (and coated first nanofibers 310) to form coated nanofiber network830 via redistribution. In one implementation, several redistributionsof active material 330 via various redistribution mechanisms may occurto allow released active material 820 to coat previously non-coatedsecond nanofibers 315. One example of a redistribution mechanism may berecrystallization.

By redistributing active material 330 to form coated nanofiber network830, electrical communication between second nanofibers 315 can beestablished within coated nanofiber network 830. This can occur beforesecond nanofibers 315 are coated to allow electrical communicationbetween second nanofibers 315 to be preserved. By preserving theelectrical communication, electrical conductivity between secondnanofibers 315 can be uninterrupted by active material 330, yet activematerial 330 coverage throughout coated nanofiber network 830 can beoptimized.

While not wishing to be bound by theory, it is believed that coatingfirst nanofibers 310 and second nanofibers 315 prior to networking maycause active material 330 to insulate junctions between nanofibers 310,315 and may prevent the nanofibers from having electrical communicationwith one another. As such, the network formation step is preferablybefore the coating or at least before the completion of the coating step(e.g., before redistribution is complete).

FIG. 9 is an example graphical illustration of charge-discharge resultsfor an example nanofiber-nanoscale active material electrode before andafter redistribution of active material 330. As illustrated in FIG. 9,nanofibers which are divided, coated, networked, and redistributed showsuperior charge and discharge properties compared to nanofibers whichare coated prior to networking. In FIG. 9, two similar samples, a firstsample with nanofibers coated with ZnCO₃, a second sample with ⅔ of thenanofibers coated with ZnCO₃, mixed with ⅓ non-coated nanofibers. Bothsamples were charged and discharged at 2 C rate (the currents, at whichthe battery is expected to be charged and discharged in ½ hour). FIG. 9shows a cycle in 30% K₂CO₃ saturated with ZnO electrolyte. One can seethat the charge curve is noisy for the first sample, pointing to poorelectrical contacts. The second sample, on the other hand, is smooth.This result, in addition to the higher potentials on the discharge curveof the second sample, appears to indicate that the second sample hasbetter electrical contacts (lower internal resistance).

Method 200 can include forming an electrode from coated nanofibernetwork 830 in step 250. In one implementation, coated nanofiber network830 can be wetted with an electrolyte. Next, wetted coated nanofibernetwork 830 can be made into a paste, and the paste can be formed intoan electrode. For example, the paste may be pressed onto a currentcollector, such as a conductive film, current collector plate, etc. Inanother implementation, coated nanofiber network 830 can be its owncurrent collector.

Additionally, as illustrated in FIG. 3F, a paste of coated nanofibernetwork 830 (or other coated nanofiber network) can be provided on acurrent collector plate 370 and a lead 380 can be attached to form anelectrode 390. In one implementation, coated nanofiber network 830 maybe wetted with the same or different electrolyte as the electrolyte usedin networking first nanofibers 310 and second nanofibers 315 in step240. Additionally, step 240 and step 250 may be done in any order, suchas forming the electrode in step 250, then redistributing the activematerial in step 240; redistributing the active material in step 240,then forming the electrode in step 250; concurrently forming theelectrode and redistributing the active material in steps 240 and 250;or may include additional intervening steps. A first and a secondelectrolyte, or a single electrolyte may be used in steps 240 and 250.

Method 200 can include repeating steps 210 to 250 to provide additionalelectrodes. In one implementation, steps 210 to 250 can be done to forman anode, then using a different active material, can be repeated toform a cathode.

FIG. 3G is an example illustration for forming a battery using theelectrode from method 200 of FIG. 2. For example, as illustrated in FIG.3G, two electrodes 390 with leads 380 can be placed in a vessel 385 withelectrolyte 395 to form a battery.

C. ELECTROLYTE SELECTION

One way of increasing the charging/discharging speed of batteries is toutilize a fast electrolyte. Aqueous electrolytes can be safe and fast,but can have limited usefulness as water decomposes at about one volt.Non-aqueous electrolytes can tolerate higher voltages, but are usuallyless conductive (i.e. slower) than aqueous electrolytes as well ashaving safety issues, such as flammability and explosiveness. In oneembodiment, the electrolyte may include an aqueous, ionically conductiveelectrolyte.

An electrolyte can be selected based upon compatibility with theelectrodes selected. Many battery chemistries, especially those withmetal anodes, also suffer from slow dissolution of active materials intothe electrolyte and/or slow self-discharge by undesirable sidereactions. Although methods to mitigate these are known, the degree ofthe problem is basically proportional to the surface area of the activematerial. Inasmuch as nanofiber electrodes have much higher surface areathan most battery electrodes, many known methods prove impracticable fornanofiber based electrodes. For example, the quantity of additive,mitigant, etc. can exceed the solubility or become otherwise impracticalfor use.

In one implementation, electrolytes may contain a carbonate, ahydroxide, a phosphate, a fluoride, and/or a sulfate. For example, KOH,NaOH, K₂CO₃, K₂SO₄, KF, NaF, Na₂CO₃, K₃PO₄, and/or H₂SO₄ may becontained in electrolytes herein.

In one implementation, a pH adjustment—using a more nearly neutralelectrolyte—may provide a solution. As used herein, a “neutral”electrolyte can include an electrolyte with a pH level between 7 and12.5. For example, an electrolyte with a bulk (i.e., overall) pH levelof 9 to 11.5 is preferred to mitigate undesirable side reactions incombination with the electrode chemistries and electrolytes discussedherein.

In one implementation, a local buffer may be added to the electrode toprovide localized pH adjustment. By providing a local buffer, causticelectrolytes (i.e., electrolytes with pH levels higher than 14), whichcan cause problems with anodes, such as the slow dissolution of activematerials, can be avoided; and electrochemical results similar toelectrodes with caustic electrolytes can be achieved using more nearlyneutral electrolytes with a local buffer. Adding local buffer can allowfor localized regions within the electrode-electrolyte system to have alocalized pH higher than 11, and thus have similar results to causticelectrolyte electrodes from neutral electrolyte electrodes.

The local buffer may be provided in solid, nanoscale form. By providinga local buffer in solid form, the solid local buffer may be provided inlocalized regions of the system in amounts exceeding the bulk solubilityof the local buffer in the electrolyte. Additionally, the local buffermay be provided in the form of nanoscale particles, which may bedistributed throughout the nanoscale coated network more easily thanlarger particles, thus allowing the local buffer to be readily availablefor the reactions of pH adjustment, while not being dissolved in theelectrolyte. Preferably, by providing a local buffer, ions may beavailable for providing hydroxide ions in a local region to raise alocal pH in an overall lower pH bulk. In one implementation, an oxide, ahydroxide, or a carbonate in solid form can be provided as a localbuffer. One example local buffer is Mg(OH)₂, which can readily providehydroxide ions, while not being dissolved by certain electrolytes.Another example local buffer is Ca(OH)₂, which can also readily providehydroxide ions, while not being dissolved by certain electrolytes.

The local buffer may be provided by depositing the local buffer solidadditive nanofibers before, after, or during the deposition of activematerial on the nanofibers. For example, the local buffer can bedeposited on a surface of the nanofibers, on a surface of the activematerial, or co-deposited with the active material.

In one implementation, in a neutral electrolyte with a bulk pH around11, a local buffer may be added to or deposited on: (1) coated firstnanofibers 310 (before or after depositing active material 330); (2)second nanofibers 315; (3) both coated first nanofibers 310 and secondnanofibers 315; and/or (4) to a system with first nanofibers 310 andsecond nanofibers 315 in step 230 to form a network.

Aqueous electrolytes, as mentioned above, can suffer from undesirableside reactions causing gas evolution. Exposed surface of the conductivesupport network may catalyze hydrogen evolution or oxygen evolution fromwater at more or less the same voltages needed to cause the desiredhalf-cell reactions. Thus, surfaces of the conductive support networkmay be desirably electrochemically insulated by covering with activematerial to reduce gas evolution and increase charge-dischargeefficiency.

Depositing additional active material may not achieve coverage of theconductive support network to reduce or prevent gas evolution. In oneembodiment herein, active material 330 may be provided such that activematerial 330 electrochemically isolates first nanofibers 310 and secondnanofibers 315, preferably when networked as coated nanofiber network830, from electrolytes. It is believed that depositing more activematerial 330 may not achieve complete coverage. Crystallization ordeposition from solution would preferentially deposit active material330 on active material 330 that is already there rather than improvingcoverage of the remaining bare surfaces of nanofibers 310, 315. Theenergy of crystal formation on the same material is usually lower thannucleation on a different material, thus the already deposited activematerial 330 can serve as a more preferable substrate for the furtherdeposition of additional material 330.

D. NANOFIBER SELECTION

As the active materials generally do not provide much, if any mechanicalsupport, nanofibers in the form of a network of nanofibers can beprovided for mechanical support of the active materials in an electrode.In addition to providing a support for the active materials, the networkof nanofibers can also be used to conduct electricity (i.e., provide apathway for electrons) from electrodes to an outside load. A network ofnanofibers can be formed by aggregating nanofibers into a randominterpenetrating network, which can provide a pathway for electrons toaccess active material supported by the random interpenetrating network.

Additionally, in order for the battery to be fast, both in charge anddischarge, none of the active material can be provided in closeproximity with a nanofiber (i.e., in contact). By providing a network ofnanofibers to support the active materials, the distance between theactive material and a nanofiber in the network of nanofibers canapproach zero to allow electrons to flow between the active material andthe nanofiber readily.

The terms “nanotube,” “fibril,” and “carbon nanotube” are usedinterchangeably to refer to single wall (i.e., only a single graphenelayer parallel to the nanotube axis) or multi-wall (i.e., more than onegraphene layer more or less parallel to the nanotube axis) carbonnanotubes or other nanoscale sized fibers. Each refers to an elongatedstructure having a cross-section (e.g., angular fibers having edges) ora diameter (e.g., rounded) of, for example for multi-wall nanotubes,less than 1 micron, less than 0.5 microns, less than 0.2 microns, lessthan 100 nm, less than 50 nm, less than 20 nm; or for example for singlewall nanotubes, less than 5 nanometers. Other types of carbon nanotubesare also known, such as fishbone fibrils (e.g., wherein the graphenesheets are disposed in a herringbone pattern with respect to thenanotube axis), “buckytubes,” etc. As produced, carbon nanotubes may bein the form of discrete nanotubes, aggregates of nanotubes (i.e., dense,microscopic particulate structure comprising entangled carbon nanotubes)or a mixture of both. Each of these conformations and structures may beused as “nanofibers” as discussed herein, as each would provideelectrically conductive, networkable structures to support activematerials.

The term “nanofiber” is broader, encompassing both nanotubes and othernano-sized fibers that may not be hollow or may lack the definedorientation of the graphenic sheets or which may be covered with anouter layer of pyrolytic carbon. Further discussion on nanofibers can befound in U.S. Pat. No. 5,800,706 and/or U.S. Pat. No. 6,099,960, whichare incorporated in their entireties by reference.

Nanofibers exist in a variety of forms and have been prepared throughthe catalytic decomposition of various carbon-containing gases at metalsurfaces. These include those described in U.S. Pat. No. 6,099,965 toTennent, et al. and U.S. Pat. No. 5,569,635 to Moy, et al., both ofwhich are hereby incorporated by reference in their entireties.

In an embodiment, nanofibers are made by catalytic growth fromhydrocarbons or other gaseous carbon compounds, such as CO, mediated bysupported or free floating catalyst particles.

Nanofibers may also be formed as aggregates of carbon nanotubes, whichmay be dense microscope particulate structures of entangled carbonnanotubes and may resemble the morphology of bird nest (“BN”), cottoncandy (“CC”), combed yarn (“CY”) or open net (“ON”).

Nanofibers may also be grown on a flat support, attached by one end tothe support and parallel to each other, forming a “forest” structure.Aggregates are formed during the production of carbon nanotubes and themorphology of the aggregate is influenced by the choice of catalystsupport. Porous supports with completely random internal texture, e.g.,fumed silica or fumed alumina, grow nanotubes in all directions leadingto the formation of bird nest aggregates. Combed yarn and open netaggregates are prepared using supports having one or more readilycleavable planar surfaces, e.g., an iron or iron-containing metalcatalyst particle deposited on a support material having one or morereadily cleavable surfaces and a surface area of at least 1 square meterper gram.

Individual carbon nanotubes in aggregates may be oriented in aparticular direction (e.g., as in “CC,” “CY,” and “ON” aggregates) ormay be non-oriented (i.e., randomly oriented in different directions,for example, as in “BN” aggregates). Carbon nanotube “agglomerates” arecomposed of carbon nanotube “aggregates.” Carbon nanotube “aggregates”retain their structure in the carbon nanotube “agglomerates.” As such,“BN” agglomerates, for example, may contain “BN” aggregates.

“BN” structures may be prepared as disclosed in U.S. Pat. No. 5,456,897,for example, which is hereby incorporated by reference in its entirety.“BN” agglomerates are tightly packed with typical densities of greaterthan 0.1 g/cc, for example, 0.12 g/cc. Transmission electron microscopy(“TEM”) reveals no true orientation for carbon nanotubes formed as “BN”agglomerates. Patents describing processes and catalysts used to produce“BN” agglomerates include U.S. Pat. Nos. 5,707,916 and 5,500,200, bothof which are hereby incorporated by reference in their entireties.

On the other hand, “CC,” “ON,” and “CY” agglomerates have lower density,typically less than 0.1 g/cc, for example, 0.08 g/cc and their TEMsreveal a preferred orientation of the nanotubes. U.S. Pat. No.5,456,897, hereby incorporated by reference in its entirety, describesthe production of these oriented agglomerates from catalyst supported onplanar supports. “CY” may also refer generically to aggregates in whichthe individual carbon nanotubes are oriented, with “CC” aggregates beinga more specific, low density form of “CY” aggregates.

Carbon nanotubes are distinguishable from commercially availablecontinuous carbon fibers. For instance, the diameter of continuouscarbon fibers, which is always greater than 1.0 micron and typically 5to 7 microns, is also far larger than that of carbon nanotubes, which isusually less than 1.0 micron. Carbon nanotubes also have vastly superiorstrength and conductivity than carbon fibers.

Carbon nanotubes also differ physically and chemically from other formsof carbon such as standard graphite and carbon black. Standard graphiteis, by definition, flat. Carbon black is an amorphous structure ofirregular shape, generally characterized by the presence of both sp2 andsp3 bonding. On the other hand, carbon nanotubes have one or more layersof ordered graphitic carbon atoms disposed substantially concentricallyabout the cylindrical axis of the nanotube. These differences, amongothers, make graphite and carbon black poor predictors of carbonnanotube chemistry.

“Multi-wall nanotubes” as used herein refers to carbon nanotubes whichare substantially cylindrical, graphitic nanotubes of substantiallyconstant diameter and comprise cylindrical graphitic sheets or layerswhose c-axes are substantially perpendicular to the cylindrical axis,such as those described, e.g., in U.S. Pat. No. 5,171,560 to Tennent, etal. The term “multi-wall nanotubes” is meant to be interchangeable withall variations of said term, including but not limited to “multi-wallnanotubes,” “multi-walled nanotubes,” “multiwall nanotubes,” etc.

“Single wall nanotubes” as used herein refers to carbon nanotubes whichare substantially cylindrical, graphitic nanotubes of substantiallyconstant diameter and comprise a single cylindrical graphitic sheet orlayer whose c-axis is substantially perpendicular to the cylindricalaxis, such as those described, e.g., in U.S. Pat. No. 6,221,330 to Moy,et al. The term “single wall nanotubes” is meant to be interchangeablewith all variations of said term, including but not limited to“single-wall nanotubes,” “single-walled nanotubes,” “single wallnanotubes,” etc.

It is understood that multiwall carbon nanotubes may be readilyfunctionalized. Methods of functionalizing nanotubes are discussed inU.S. Pat. Nos. 6,203,814, 7,413,723, and 6,872,681, which areincorporated by reference in their entireties. Such functionalizedmultiwall carbon nanotubes may be more readily dispersed in aqueousmedia than as-made, non-functionalized multiwall carbon nanotubes.Either functionalized or as-made nanotubes may be used herein.

Generally, functionally modified nanotubes may aggravate side reactionsof an aqueous electrolyte with the functionally modified nanotubes.However, the functional groups on the surface may be beneficial forbetter adherence of active material 330 to a nanofiber. In oneimplementation, the step of redistributing active material on coatednanofiber network 830 may be helped by functional groups. After theredistribution, the nanofibers will no longer be in direct contact withelectrolyte (as the nanofibers will be coated); therefore side reactionsmay be minimized. The conductivity of nanofiber networks depends notonly on the inherent conductivity of the nanofibers, but also upon theaverage length and spatial density of the fibers in the network. Networkresistance is believed to derive mainly from the fiber-fiber resistanceat the intersections.

E. ACTIVE MATERIAL SELECTION

The terms “active material” and “electroactive agent” are usedinterchangeably to refer to chemical compounds that provide chemicalenergy for conversion to electrical energy in a battery. The activematerial may be an electrochemically active material in that it may be asubstance that can participate in the release or acceptance of anelectron. The active material may also be provided on a nanoscale level.In one embodiment, the active material may be electrochemically activenanoscale solid substances, such as nanoscale sized particles ofelectrochemically active material.

The choice of active material for a battery depends on factors otherthan energy density and power density. These include, but are notlimited to: cost, safety, life, reliability, temperature stability,failure mode, etc. In embodiments provided herein, electrodes areprovided that can improve the power density of any battery system orindividual electrode. Electrode chemistries known to be reversible are,however, preferred. These include, but are not limited to NiOOH/Ni(OH)₂;Zn/ZnOH; Cd/Cd(OH)₂; Fe/Fe(OH)₂; Pb/Pb(OH)₂; Pb/PbSO₄; MnO₂/Mn₂O₃;PbO₂/PbSO₄; Co/Co(OH)₂; Ag/AgO; Al/Al₂O₃; Mg/Mg(OH)₂, Metal/MetalHydride; etc.

In one embodiment, the active material may be provided by depositing theactive material in nanoscale sized form from solution. In oneembodiment, the active material may be nanoscale solid material afterdeposition on a nanofiber.

Additionally, the active material, upon application, may provideinsulation from an electrolyte in an electrode, as described herein. Inone embodiment, the active material may reduce or prevent interactionbetween the nanofibers and electrolyte in an electrode. For example, byutilizing the methods provided herein, side reactions between thenanofibers and the electrolyte may be reduced by the presence of theactive material insulating the nanofibers from the electrolyte.

Systems compatible with an aqueous electrolyte are also preferredbecause aqueous electrolytes can better exploit the energy density ofthe batteries described herein.

F. ELECTRODE FORMATION

In embodiments herein, electrodes can be made or provided in the form ofa two dimensional sheet or mat. If a two dimensional sheet is provided,then the sheet may be assembled into a device with a current collector.For example, a current collector can be provided in the form of a foilor conductive layer aligned in parallel to the electrode and in intimatecontact therewith. The through sheet conductivity of the electrode mustbe high enough not to limit the power density of the battery.

If a three dimensional mat is provided, then the mat may have athickness as desired. While the performance of the electrode may varywith the thickness of the active material, such variations may alsooccur based upon different active materials.

In one embodiment, a coated nanotube network electrode can function asits own current collector. In this case, the coated nanotube networkelectrode can be connected to an outside load (or to other cells in thestack) through its edges, which causes the conductivity in the directionof the electrode plane (the x-y conductivity) to become critical to thecell resistance. This cell resistance may be less 200 ohms-cm, morepreferably less than 100 ohms-cm, and still more preferably less than 50ohms-cm.

G. EMBODIMENTS

In one embodiment, a nanofiber-MnO₂ electrode can be paired with ananofiber-Zn electrode to provide a pair of fast fibril (nanofiber)electrodes in a battery. In other embodiments, electrodes withnanofibers and compounds of Zn, Co, Cd, Fe, and/or Pb can be paired withelectrodes with nanofibers and compounds of Ni to provide fast fibrilelectrodes.

In one embodiment, a nanofiber electrode may contain more activematerial than nanofibers to allow for more active material to be presentin an electrode. For example, a nanofiber electrode may contain lessthan 50 wt. % nanofibers. In another example, a nanofiber electrode maycontain less than 25 wt. % nanofibers, which may also include more than75 wt. % active material.

In one embodiment, a nanofiber electrode can have a porosity level thatallows enough electrolyte to complete charge and discharge withoutprecipitation. For example, a nanofiber electrode may contain a networkwith a volume of porosity of 50 to 90 vol. %, which can allow forsufficient levels of electrolyte to complete charge and dischargewithout precipitation. As another example, a nanofiber electrode maycontain a network with a volume porosity of 50 to 80 vol. % to increasethe electrode volume devoted to active ingredients, as porosity reduceselectrode volume that could be devoted to active material.

In one embodiment, active materials 330 and electrolytes, in combinationwith the nanofiber electrode, may be chosen such that a charge-dischargeefficiency can be greater than 90%. In another embodiment, activematerials 330 and electrolytes, in combination with the nanofiberelectrode, may be chosen such that a charge-discharge efficiency can begreater than 95%. For example, an electrode with Zn active material 330with a K₂CO₃ electrolyte may provide a charge-discharge efficiencygreater than 90% (as discussed further below).

It should be recognized that embodiments herein are describing theelectrochemical aspects of the preferred electrodes. Other componentsmay be added to the paste or mat for the electrodes to alter physical orelectrical properties. Binders, additives to improve conductivity, cyclelife, thermal stability, charge retention, shelf life, structuralintegrity, or other parameters may be employed. Generally, the quantityof additives should be small enough not to materially alter the energyor power density of the electrodes. For example, additives maypreferably be added at less than 20 wt. % of the electrode, morepreferably less than 10 wt. % of the electrode, and even more preferablyless than 5 wt. % of the electrode. Examples of additives can be foundin U.S. Pat. No. 6,790,559 (e.g., additives to Ni electrode: fluoridesalts 0.1-1% for active material utilization) and U.S. Pat. No.6,811,926 (e.g., additives to Zn electrodes: inorganic fibers (aluminaand silica, 2-15%) and bismuth oxide (2-10%) for cycle life), both ofwhich are incorporated by reference in their entireties.

In one embodiment, asymmetrical electrodes may be used in an energystorage device. For example, a nanofiber electrode provided herein maybe combined with a traditional electrode to modify an existing battery.As another example, a nanofiber electrode provided herein may becombined with an electrochemical capacitor (i.e., supercapacitor)electrode to modify an existing supercapacitor.

H. EXAMPLES Example 1—Method of Making an Electrode

Initially, active material 330 can be introduced into a network formingstep by a prior “rough” deposition onto only a fraction of thenanofibers, in an aqueous electrolyte whose anion forms only a sparinglysoluble salt, NiCO₃ or ZnCO₃, for example, with a cation of activematerial 330. A sparingly soluble salt may be any salt with solubilityless than 1 g/100 g, but greater than zero. In one embodiment, thesparingly soluble salt may have solubility greater than zero and lessthan 0.1 g/100 g. For example, the sparing soluble salt may include, butis not limited to hydroxides, carbonates, fluorides, sulfates, oxalates,phosphates.

The sparingly soluble salt may be provided as an intermediate to assistin any redistribution of coating. If the sparingly soluble salt has beenprior deposited onto a fraction of the nanofibers, then the networkforming step can include both “roughly coated” and “plain”(non-coated/un-deposited) nanofibers.

Using method 200 described above, first nanofibers 310, preferablynon-oxidized nanofibers, can be provided in a liquid vehicle that mayinclude a readily soluble salt, such as Ni(NO₃)₂ or ZnSO₄, for example.Non-oxidized or oxidized fibers may be used. Further discussion ofnon-oxidized and oxidized fibers can be found in U.S. Pat. No.7,413,723, which is incorporated in its entirety by reference.

A readily soluble salt as used herein may be any soluble compound thatcan form a sparingly soluble compound of the desirable chemistry.Chlorides, nitrates, bicarbonates, some sulfates, and other solublesalts may be used for the step of deposition of active material 220 ofmethod 200. Next, a reactant, such as K₂CO₃ or KOH, can be added to theliquid vehicle, which includes a soluble salt, and the reactant cancombine with the soluble salt to deposit the corresponding sparinglysoluble salt on coated nanofibers 310. This sparingly soluble salt canbecome active material 330 after step 240 in method 200, discussedabove.

Next, a repeated charge and discharge may be applied to a network ofcoated nanofibers 310 and non-coated nanofibers 315 in an appropriateelectrolyte to redistribute active material 330 over all the nanofibers310, 315 to form a coated nanofiber network 830.

Optionally, a “local buffer” can be provided in coated nanofibers 310,non-coated nanofibers 315, or both. In one implementation, the localbuffer can be deposited together with the sparingly soluble salt (thatwill become active material 330), or before or after depositing thesparingly soluble salt.

In one implementation, the local buffer may include an oxide, ahydroxide, or a carbonate. For example, the local buffer may include anoxide, a hydroxide, or a carbonate of Mg or Ca. As another example, thelocal buffer may include Mg(OH)₂ or Ca(OH)₂. In one embodiment, thelocal buffer may be Mg(OH)₂ and the active material for the twoelectrodes may be Ni(OH)₂ and Zn(OH)₂, respectively.

Co-depositing active material 330 and the local buffer can improveelectrode performance, which can be measured by % charge recovery. Inone implementation, a local buffer may be co-deposited with activematerial 330 on nanofibers 310, deposited on nanofibers 310 after activematerial 330, deposited on nanofibers 315, or deposited on both coatednanofibers 310 and nanofibers 315. In one implementation, a local buffermay be added in amounts of 20% to 100% chemical equivalent to the amountof active material 330.

While not wishing to be bound by theory, a local buffer, such asMg(OH)₂, may create a locally increased pH within a network ofnon-coated nanofibers, which in turn may improve the performance of ahalf-cell reaction, such as Ni(OH)₂ oxidation or Zn(OH)₂ reduction. Onthe Zn side the increased pH may favor Zn reduction over hydrogenevolution, while on the Ni side, the locally increased pH may allow thecharge process to operate in a more neutral electrolyte than aconcentrated caustic electrolyte, which can alternatively be used.

Additionally, a different electrolyte may be used for electrodepreparation than for cell use. In one embodiment, a concentrated causticelectrolyte (i.e., a pH greater than 14), such as KOH, can be used forelectrode preparation and a different, more neutral electrolyte (i.e., apH between 7 and 12), such as K₂CO₃, can be used for cell use. In oneimplementation, an electrolyte for electrode assembly can be selectedbased on solubility of the intermediate salt, while another electrolytefor cell use can be selected based on the stability of the activematerials. For example, Ni(OH)₂ electrodes may be removed from a KOHelectrode preparation electrolyte solution and transferred to acarbonate electrolyte for cell use. In another embodiment, a neutralelectrolyte, such as K₂SO₄, may be used for preparation of PbSO₄electrode, and a different electrolyte, such as H₂SO₄, may be used forcell use.

Example 2—Method of Making a Battery

In one embodiment, a Ni—Zn battery with a carbonate electrolyte isprovided.

A Ni electrode material of nanofibers and active material was preparedas follows:

-   -   a. 30 mg of CC morphology nanofibers were sonicated in 100 ml        deionized (DI) water with 2 drops of Triton X100™ surfactant.    -   b. ⅓ of the suspension was left aside.    -   c. 3 mM Ni(NO₃)₂*6H₂O and 1.5 mM MgCl₂ were dissolved in the ⅔        of the suspension.    -   d. 4.5 mM K₂CO₃ were dissolved in 10 ml DI water and added        drop-by-drop to the suspension to precipitate NiCO₃ and MgCO₃.    -   e. The mixture was brought to boil, then cooled to facilitate        precipitation of MgCO₃.    -   f. The ⅓ of the suspension that was left aside, which contains        non-coated nanofibers were added to the ⅔ of the suspension        (i.e., the suspension containing NiCO₃ and MgCO₃ precipitate)        and stirred, then filtered on a nylon membrane.    -   g. The remaining material removed from the filtration was dried        at 120° C.    -   h. The material exhibited a weight gain of 401 mg of which is        estimated to be about 126 mg MgCO₃ (1.5 mM) and about 275 mg        NiCO₃ (2.3 mM).

The Zn electrode material was prepared as follows:

-   -   a. 20 mg CC fibrils were sonicated in 100 ml DI water with 2        drops of Triton X-100™ surfactant.    -   b. ⅓ of the suspension was left aside.    -   c. 1.5 mM ZnSO₄ were added to the ⅔ of the suspension and        precipitated drop-by-drop with 1.5 mM K₂CO₃ (dissolved in 10 ml        DI water).    -   d. 1.5 mM MgCl₂ were added to the suspension and precipitated        drop-by-drop with 3 mM KOH (dissolved in 10 ml DI water).    -   e. The remaining ⅓ of the fibrils were added, stirred well and        filtered on a nylon membrane.    -   f. The material was dried at 120° C.    -   g. The material exhibited a weight gain of 225 mg which is        estimated to be about 87 mg Mg(OH)₂ (1.5 mM) and about 138 mg        ZnCO₃ (1.1 mM).

The Ni electrode was prepared as follows:

-   -   a. Nickel material (40 mg→0.21 mM Ni, C rate=5.7 mA) was wetted        with 30% KOH and crushed into a paste.    -   b. The paste was placed in a single electrode cell with a        conductive film as a current collector (backed up by a nickel        plate).    -   c. The electrode was charged and discharged twice in 30% KOH        electrolyte at ˜2 C rate with a Pt plate as a counter-electrode.        The second discharge gave 84% of the theoretical capacity. See        FIG. 10, which is an example graphical illustration of discharge        results for an example nanofiber-nanoscale Ni electrode. If        repeated several more times (not shown here), the        charge-discharge efficiency would approach 100%, which indicates        that practically no side reaction of water decomposition and        oxygen evolution takes place on a thusly prepared electrode.    -   d. Without taking the electrode from the cell, it was rinsed        with DI water.

The Zn electrode was prepared as follows:

-   -   a. Zn material (23 mg→0.10 mM Zn, C rate=5.5 mA) was wetted with        electrolyte (30% K₂CO₃, saturated with ZnO).    -   b. The material was placed in a single electrode cell with        conductive film as a current collector (backed up by a nickel        plate).    -   c. The electrode was charged and discharged once at 2 C rate        with a Pt plate as a counter-electrode. The discharge gave 94%        of the theoretical capacity. See FIG. 11, which is an example        graphical illustration of discharge results for an example        nanofiber-nanoscale Zn electrode.    -   d. The Pt plate and the reference electrode (Ag/AgCl) were        removed from the cell, and the nickel electrode was placed in        the beaker instead.    -   e. The cell was charged at a constant current of 2 C rate for        the first 6 cycles, and then at different constant voltages.

The Zn—Ni electrodes in the separate fixtures gave 70% capacity at 2 Crate. FIG. 12 is an example graphical illustration of discharge resultsfor example nanofiber-nanoscale electrodes after 2 charge-dischargecycles as separate electrodes, 9 charge-discharge cycles as separateelectrodes, and 18 charge-discharge cycles as a battery cell (i.e.,combined electrodes).

It can be seen in FIG. 12 that at around the 1V cutoff voltage thebattery is not fully discharged. To see the full capacity, following thedischarge at 2 C rate, the battery was discharged at 0.2 C rate (thecutoff voltage was kept at 1V). In the second cycle, full returnedcapacity was 74%, in the 9^(th) cycle—82%. However, the voltage wasdeteriorating, because the charge efficiency in the first cycles was nothigh enough. It started at ˜85%, and it came up to 90% in the 10^(th)cycle.

It is believed that additional cycles may allow for an individual chargeefficiency closer to 100%.

After the 13^(th) cycle, 30 minutes were allowed to pass between thecharge and the discharge, and the result was compared with the returnedcapacity of the 12^(th) cycle, which had no delay. The amount of chargewas the same for these two cycles. The difference between total returnedcapacities in these two cycles was less than 4%.

After the 14^(th) cycle, the samples were placed in the battery cell. InFIG. 12, a discharge curve of the battery is illustrated at 2 C rate. Inthe process of moving the samples, some capacity appeared to be lost,but the voltages, as expected, improved.

The above example illustrates a Ni—Zn battery which utilizes twoelectrodes formed from coated nanofibers and a relatively neutralelectrolyte. The Ni—Zn battery can exhibit high power characteristicsdue to the nanoscale nature of the active material, as well as highstability of the electrodes in the chosen electrolyte.

A nanofiber/NiOOH electrode and a nanofiber/Zn electrode can be madethat are capable of high rate charge and discharge. However, in astandard 30% KOH electrolyte the Zn electrode can be unstable, and candissolve as a zincate ion quickly. In order to overcome this problem, aless active 30% K₂CO₃ electrolyte can be used. Zn is expected to be muchmore stable in the absence of the excess of OH⁻ ions. Yet, the hydroxylions can be used for the charge cycle of the battery.

On the anode side, the higher the pH, the lower amount of H₂ is formed,since the potential of hydrogen evolution directly depends on the pH ofthe electrolyte. On the cathode side, acid may be formed during thecharge, which may need neutralization to prevent or reduce the effectsof the acid on the Ni active material and also to reduce conversion ofcarbonate ions to CO₂ gas. In order to provide OH⁻ ions, Mg(OH)₂ can beadded to the active material. Magnesium hydroxide, as well as magnesiumcarbonate, may not be soluble in the electrolyte, and would be expectedto transform back and forth without leaving the places of initialdeposition.

In one example battery, the battery may include two electrodes withdifferent electrode chemistries. In this implementation, one of the twoelectrodes may include nanofibers, such as carbon nanotubes. In thisimplementation, the nanofiber containing electrode may have a volumeporosity greater than 50%, 60%, 70%, or 80%. Additionally, the nanofibercontaining electrode may include less than 25 wt. %, 20 wt. %, 15 wt. %,or 10 wt. % nanofibers.

Additionally, the battery, when discharged at ambient conditions at a 1C rate, may have a cell voltage greater than 80%, 85%, 90%, or 95% ofthe theoretical voltage. Additionally, the battery may have a rechargeefficiency when recharged at 2 C rate greater than 95%, 98%, or 99%. Thebattery may also include an electrolyte that has a pH below 12.5, whichmay contain K₂CO₃. The nanofiber containing electrode may also notinclude a current collector separate from the nanofibers in theelectrode. Additionally, the two electrodes may be an electrodecontaining a Ni compound or an electrode containing a Zn compound.

Electrodes described herein may be used in batteries. The electrodes canbe provided in single-use, non-rechargeable batteries (often referred toas “primary batteries”) or multiple use, rechargeable batteries (oftenreferred to as “secondary batteries”). The electrodes can also beprovided in flexible batteries, or other types of batteries.

While the invention has been described in detail with reference topreferred embodiments thereof, it will be apparent to those skilled inthe art that variations and modifications can be made, and equivalentsemployed without departing from the scope of the appended claims.

What is claimed is:
 1. A battery, comprising: two electrodes; and anelectrolyte, wherein at least one electrode comprises: a nano-scalecoated network, comprising: one or more first carbon nanotubeselectrically connected to one or more second carbon nanotubes to form anano-scale network, wherein at least one of the one or more secondcarbon nanotubes is in electrical contact with another of the one ormore second carbon nanotubes; and an active material coating formed bycovering and redistributing the active material coating, wherein theactive material coating is formed by covering portions of the one ormore first carbon nanotubes and not portions of the one or more secondcarbon nanotubes, wherein the active material coating is redistributedfrom the covered portion of the one or more first multi-wall carbonnanotubes to the not covered portion of the one or more secondmulti-wall carbon nanotubes.
 2. The battery of claim 1, wherein thebattery, when discharged at ambient conditions at a 1 C rate, has a cellvoltage greater than 80% of the theoretical voltage and/or a rechargeefficiency, when recharged at a 2 C rate, of greater than 95%.
 3. Thebattery of claim 1, wherein the electrolyte comprises an aqueoussolution with a pH below 12.5.
 4. The battery of claim 1, wherein theactive material coating includes a compound of Zn, Cd, Co, Ni, Fe, Pb,Al, Mn, or Ag.
 5. The battery of claim 1, further comprising a secondelectrode, wherein the first electrode comprises an active materialcomprising at least a compound of Ni, and the second electrode comprisesan active material comprising at least a compound of Zn, and wherein theelectrolyte comprises an aqueous solution.
 6. The battery of claim 1,wherein the active material coating is redistributed by electricalcharge and discharge of the active material coating, or recrystallizingthe active material coating.
 7. An electrochemical capacitor comprising:a first electrode comprising: a nano-scale coated network, comprising:first carbon nanotubes; second carbon nanotubes; and an active materialcoating, wherein the first carbon nanotubes are electrically connectedto second carbon nanotubes to form a nano-scale network, wherein atleast a first of the second carbon nanotubes is in electrical contactwith a second of the second carbon nanotubes; wherein the activematerial coating covers portions of the first carbon nanotubes andportions of the first of the second carbon nanotubes, and wherein a thefirst of the second carbon nanotubes is in direct physical contact withsecond of the second carbon nanotubes under the active material coatingcovering the portion of the first of the second carbon nanotubes; asecond electrode; and an electrolyte.
 8. The electrochemical capacitorof claim 7, wherein the active material coating is redistributed from asurface of a first multi-wall carbon nanotube to a surface of a secondmulti-wall carbon nanotube, and wherein the second multi-wall carbonnanotube is in direct contract with another second multi-wall carbonnanotube.
 9. The electrochemical capacitor of claim 8, wherein theactive material coating is treated using electrical charge and dischargeto form the first electrode, or recrystallization to form the firstelectrode.
 10. The electrochemical capacitor of claim 7, wherein theelectrolyte comprises an aqueous solution with a pH below 12.5.
 11. Theelectrochemical capacitor of claim 7, wherein the active materialcoating includes a compound of Zn, Cd, Co, Ni, Fe, Pb, Al, Mn, or Ag.12. A method of forming a battery, comprising: forming a first electrodecomprising: providing first carbon nanotubes; providing second carbonnanotubes; coating the first carbon nanotubes with a nanoscale substanceto form coated carbon nanotubes; forming a network of the coated carbonnanotubes and the second carbon nanotubes; providing a firstelectrolyte; and redistributing the nanoscale substance from a surfaceof one of the coated carbon nanotubes to a surface of one of the secondcarbon nanotubes within the network in the first electrolyte to form thefirst electrode; providing a second electrolyte; providing a secondelectrode; and providing the first and the second electrode in thesecond electrolyte to form a battery, wherein the first electrolyte andthe second electrolyte are different electrolytes.
 13. The method ofclaim 12, wherein the coating the first carbon nanotubes with ananoscale substance comprises coating the first carbon nanotubes with anelectrochemically active nanoscale solid substance.
 14. The method ofclaim 13, wherein coating the first carbon nanotubes with anelectrochemically active nanoscale solid substance comprises coating thefirst carbon nanotubes with a compound of Ni, Zn, Cd, Fe, Pb, Mn, Co,Ag, Al, or Mg.
 15. The method of claim 13, wherein coating the firstcarbon nanotubes with an electrochemically active nanoscale solidsubstance comprises coating the first carbon nanotubes with one or moreof hydroxides, carbonates, fluorides, sulfates, oxalates, phosphates.16. The method of claim 12, wherein the coating the first carbonnanotubes with a nanoscale substance comprises depositing the nanoscalesubstance from a solution on to the first carbon nanotubes.
 17. Themethod of claim 12, wherein the providing the first electrolyte and/orthe second electrolyte comprises providing an aqueous, ionicallyconductive electrolyte.
 18. The method of claim 12, wherein theproviding the second electrolyte comprises providing an electrolyte witha pH level between 7 and 12.5.
 19. The method of claim 12, wherein theproviding the second electrolyte comprises providing an electrolytecontaining a carbonate, a fluoride, a phosphate, and/or a sulfate. 20.The method of claim 12, wherein the providing the second electrolytecomprises providing an electrolyte containing K₂CO₃, K₂SO₄, KF, NaF,and/or K₃PO₄.
 21. The method of claim 12, further comprising providingone or more of an oxide, a hydroxide, or a carbonate in solid form tothe step of providing first carbon nanotubes, to the step of providingsecond carbon nanotubes, or to the step of coating the first carbonnanotubes with a nanoscale substance to form coated carbon nanotubes.22. The method of claim 21, wherein the providing one or more of theoxide, the hydroxide, or the carbonate in solid form comprises providingone or more of an oxide, a hydroxide, or a carbonate of Mg or Ca insolid form.
 23. The method of claim 21, wherein the providing one ormore of the oxide, the hydroxide, or the carbonate in solid formcomprises providing Mg(OH)₂ or Ca(OH)₂ in solid form.
 24. The method ofclaim 21, wherein the providing one or more of the oxide, the hydroxide,or the carbonate in solid form comprises depositing the oxide, thehydroxide, or the carbonate in solid form on the first carbon nanotubes,the second carbon nanotubes, or both the first carbon nanotubes and thesecond carbon nanotubes.
 25. The method of claim 21, wherein theproviding one or more of the oxide, the hydroxide, or the carbonate insolid form comprises: depositing the one or more of the oxide, thehydroxide, or the carbonate in solid form on a surface of the firstcarbon nanotubes or on a surface of the nanoscale substance, orco-depositing the one or more of the oxide, the hydroxide, or thecarbonate in solid form and the nanoscale substance on the first carbonnanotubes.